The rate constant of ligand exchange on the complex fac-[(99)Tc(H(2)O)(3)(CO)(3)](+) was determined by means of (13)C, (17)O, and (99)Tc NMR spectroscopy under pressurized conditions in aqueous media. After keeping the sample under CO pressure for an extended period, the formation of [(99)Tc(CO)(6)](+) could unambiguously be detected in the (13)C and (99)Tc NMR spectra.